JP2013163676A - Low-melting mixture of di-n-butyl terephthalate and diisobutyl terephthalate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a terephthalic acid diester composition having a lowered freezing point.SOLUTION: A composition contains n-butyl isobutyl terephthalate, di-n-butyl terephthalate, and diisobutyl terephthalate. The composition is produced by bringing an n-butanol, isobutanol, and dimethyl terephthalate into contact with one another in an amount of 0.5:1.0 to 4.0:1.0 molar ratio of the n-butanol/isobutanol, in the presence of a catalyst.

Description

  The present invention relates to n-butylisobutyl terephthalate and a terephthalic acid diester mixture having a low melting point. The invention also relates to the preparation of a mixture of n-butylisobutyl terephthalate and terephthalic acid diester.

  Terephthalic acid diesters such as di-n-butyl terephthalate (DBT) and isobutyl terephthalate (DiBT) can be used as plasticizers in various polymeric materials such as polyvinyl chloride. However, di-n-butyl terephthalate (DBT) has a melting point of about 16 ° C. Similarly, pure diisobutyl terephthalate solidifies at an even higher temperature of 54 ° C.

  This could lead to the problem that these products solidify on storage at low temperatures. Such product solidification often requires the installation of heating tanks, transfer lines and associated handling equipment, thus increasing the cost of use of these products. The present invention addresses this problem by producing terephthalic acid diesters having lower melting points.

  The first aspect of the present invention relates to a composition comprising n-butylisobutyl terephthalate.

  Another aspect relates to a plasticizer comprising n-butylisobutyl terephthalate.

  A third aspect relates to a process for producing n-butylisobutyl terephthalate comprising contacting n-butanol, isobutanol and dimethyl terephthalate in the presence of a catalyst.

  Yet another embodiment comprises contacting the first alcohol, the second alcohol and dimethyl terephthalate in the presence of a catalyst, wherein the first alcohol and the second alcohol are different terephthalic acid diesters. The present invention relates to a method for producing a mixture.

2 shows a DSC melting point analysis of pure DBT. Figure 2 shows a DSC melting point analysis of DBT: DiBT75: 25. Figure 2 shows a DSC melting point analysis of DBT: DiBT50: 50. Figure 2 shows a DSC freezing point analysis of DBT: DiBT75: 25. Figure 2 shows a DSC freezing point analysis of DBT: DiBT50: 50. Figure 2 shows a second DSC melting point analysis of DBT: DiBT75: 25. Figure 2 shows a second DSC melting point analysis of DBT: DiBT50: 50. 2 shows DSC freezing point analysis of pure DBT.

  The present invention relates to the preparation of n-butylisobutyl terephthalate and a terephthalic acid diester mixture having a low melting point. This mixture comprises 1) di-n-butyl terephthalate; 2) n-butyl isobutyl terephthalate; and 3) isobutyl terephthalate. In general, the reaction for forming n-butylisobutyl terephthalate and / or terephthalic acid diester mixture can be represented by the following formula.

  To produce n-butylisobutyl terephthalate and / or terephthalic acid diester mixture, the n-butanol / isobutanol mixture is dimethyl terephthalate (DMT) in the presence of a transesterification catalyst using a batch reactor or a continuous reactor. Can be reacted. For example, the reactor can be equipped with a simple distillation column and an inlet for charging DMT, alcohol mixture and catalyst. In practice, the reactor is charged with catalysts such as DMT, various molar ratios of n-butanol / isobutanol and catalytic amounts of tetraisopropoxy titanate (TIPT). Heating and stirring the mixture to reflux produces methanol by transesterification, which is selectively removed at the top of the distillation column. Conversion to an n-butanol / isobutanol mixture is essentially complete in 6-8 hours. The crude product can then be stripped of excess unreacted alcohol mixture and treated with 2.5% NaOH to cool the titanate catalyst, washed with water, and dried in vacuo at reduced pressure. Activated carbon treatment can be used to reduce the color in the final product.

The catalyst used in this process is a transesterification catalyst. Further, the catalyst can be a compound that is soluble in the reaction mixture, ie, soluble in the alcohol and terephthalic acid diester products. For example, the catalyst can be a titanium catalyst. Examples of suitable titanium compounds include titanium tetraalkoxides having the formula Ti (OR) _{4 where} R is an alkyl group having 1 to 8 carbon atoms. An example is tetraisopropoxy titanate, commonly abbreviated as TIPT. A catalytically effective amount of titanium compound is generally an amount that provides a titanium [Ti] concentration range of about 10 to 2000 ppm, 75 to 1000 ppm, or 100 to 200 ppm by weight in the reaction mixture. Other suitable catalysts include titanium tetrabutoxide, tin tetraethoxide, dimethyltin acetate, titanium oxide, butyl stanoic acid, dibutyltin oxide and zirconium tetraisopropoxide.

  The mixture can also be produced by mixing two pure diesters, adding a TIPT transesterification catalyst and heating. Higher molecular weight alcohols that are converted to dialkyl terephthalates, considered to be waxes or solids at room temperature, could be converted to mixed esters to produce lower melting complex products.

  This method can be used at molar ratios of about 0.5: 1.0 to about 4.0: 1.0 or about 0.75: 1.0 to about 3.0: 1.0 or even about 1.0: 1. It can be carried out with n-butanol / isobutanol ranging from 0.0 to about 2.0: 1.0.

  Unreacted alcohol mixture can be easily recycled to the process. This process can be carried out in continuous mode by adding DMT in molten form to a suitable reactor, the alcohol / TIPT mixture being fed by a separate pump to a stirred reactor fitted with a column, and methanol from the reaction is fed. Remove and allow unreacted higher alcohol to return to the reactor at reflux. The effluent from this reactor can be transferred to a series of one or more finishing reactors where conversion to an ester mixture is continued while removing methanol. The product of this reaction can be further processed and purified by processes consistent with those described in the batch examples.

  In the following examples, the equipment used consisted of a 1 liter base equipped with a heating mantle, a magnetic stir bar, temperature sensor and a 10 "Penn State packed distillation column. A variable-speed take-off head is installed that allows automatic removal.

  Each example was performed by carrying out the reaction under reflux under typical reaction conditions, while simultaneously removing methanol with a packed column at a take-up ratio of 1: 4. Upon completion of the reaction, the fractionation column was then replaced with a 3 "Vigreux column and a vacuum was applied to a final pressure of 18 mm Hg before stripping excess alcohol from the base. The crude product was 2.5% NaOH. Treated with aqueous solution to neutralize the TIPT catalyst and washed twice with deionized water, then the material was suction filtered through a glass fiber filter circle coated with Dicalite filter aid. Dried at 1 mm Hg at a final base temperature of about 120 ° C. and held for 1 hour After cooling to 90 ° C., activated carbon (0.2 wt%) was added and held at that temperature with stirring for 1 hour. Was isolated by filtration through a glass fiber filter coated with Dicalite filter aid.

Example 1
The reaction was carried out according to the reaction formula shown generally above and was designed to produce a product derived from a 50:50 mol% mixture of n-butanol and isobutanol.

  In the reactor system, 436.9 g of dimethyl terephthalate (2.25 mol, MW = 194.19), 207.5 g of n-butanol (2.8 mol, MW = 74.12), 207.5 g of isobutanol (2.8 mol, 2.8 mol, MW = 74.12) and tetraisopropoxy titanate (TIPT) 223 ppm (0.19 g). The progress of the reaction is summarized in Table I below:

  The product was stripped as summarized in Table II below.

  After neutralization, drying, carbon treatment and final filtration according to the general work-up procedure described above, the isolated product weighed 547.7 g. The theoretical amount of product was 626.28 g and the isolated yield was 87.5%.

Example 2
The reaction described in Example 1 was repeated to produce a product derived from a 75:25 mol% mixture of n-butanol and isobutanol. In the reactor system, 233 g of dimethyl terephthalate (1.2 mol, MW = 194.19), 200.1 g of n-butanol (2.78 mol, MW = 74.12), 66.7 g of isobutanol (0.9 mol, MW =) 74.12) and 220 ppm (0.11 g) of TIPT were charged. The progress of the reaction is summarized in Table III below:

  The product was stripped as summarized in Example 1 above and isolated as a clear liquid after neutralization, drying, carbon treatment and final filtration.

Example 3
The reaction described in Example 1 was repeated to produce a product derived from a 25:75 mol% mixture of n-butanol and isobutanol. In the reactor system, 233 g of dimethyl terephthalate (1.2 mol, MW = 194.19), 66.7 g of n-butanol (0.9 mol, MW = 74.12), 200.1 g of isobutanol (2.7 mol, MW =) 74.12) and 280 ppm (0.14 g) of TIPT were charged. The progress of the reaction is summarized in Table IV below:

  The product was stripped as summarized in Example 1 above and isolated as a partially solid material after neutralization, drying, carbon treatment and final filtration. Since the objective was to develop a product with a lower freezing point, no further work was done on this material.

  Each sample was analyzed by capillary gas chromatography (uncorrected area% value reported). The results are summarized in Table V below:

Freezing point analysis Two of the substances (158-01, 163-01) were subjected to DSC point analysis together with pure DBT. This analysis employed a heat-cool-heat cycle in a sealed stainless steel pan. The scan rate was 2 ° C./min in helium. FIG. 1 is a warm-up cycle for pure DBT.

The results show complex freezing point behavior. For a 75:25 DBT / DIBT mixture:
During the first warm-up, there are two crystallization events at -66 ° C and -42 ° C, followed by a small melting event at -5 ° C and a large melting event at 6 ° C.

  During the second warm-up, there are two crystal events at -35 ° C and -29 ° C followed by a small melting event at -5 ° C and a large melting event at 6 ° C.

  3. The freezing point peaked at about -42 ° C (supercooled).

For a 50:50 mixture,
1. The freezing point reached a peak at about −22 ° C. (supercooled).

  During the second warm-up, two low temperature events (crystallization at −56 ° C. and melting at −17 ° C.) are followed by another melting at −6 ° C. and a final melting at 8 ° C.

  3. During the second warm-up, it goes through a crystallization event at -15 ° C and a melting event at -8 ° C, followed by a small melting event at 10 ° C.

  Of the two, the 50:50 mixture looks best in that there is a smaller melting event in the warmer region (75: versus 50:50 for a small event at 8-10 ° C). There is a big event at 6 ° C for 25 mixtures). On the other hand, the 75:25 mixture appears to be supercooled to a lower temperature than the 50:50 mixture (−42 ° C. versus −22 ° C.).

  Note that DBT was supercooled to -7 ° C. prior to solidification, as shown in FIG.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
The embodiments of the present invention are listed below.
Aspect 1. A composition comprising n-butylisobutyl terephthalate.
Aspect 2. The composition according to embodiment 1, further comprising di-n-butyl terephthalate and diisobutyl terephthalate.
Aspect 3. A plasticizer comprising n-butylisobutyl terephthalate.
Aspect 4. The plasticizer according to embodiment 3, further comprising di-n-butyl terephthalate and diisobutyl terephthalate.
Aspect 5 A method for producing n-butylisobutyl terephthalate, comprising contacting n-butanol, isobutanol and dimethyl terephthalate in the presence of a catalyst.
Aspect 6 The process according to embodiment 5, wherein the catalyst is a transesterification catalyst.
Aspect 7. The process according to embodiment 6, wherein the catalyst is tetraisopropoxy titanate.
Aspect 8 The method of embodiment 5, wherein the n-butanol and isobutanol are present in an n-butanol / isobutanol molar ratio of about 0.5: 1.0 to about 4.0: 1.0.
Aspect 9. The method of embodiment 8, wherein the n-butanol and isobutanol are present in an amount of n-butanol / isobutanol molar ratio of about 0.75: 1.0 to about 3: 1.0.
Aspect 10 The method of embodiment 9, wherein said n-butanol and isobutanol are present in an amount of n-butanol / isobutanol molar ratio of about 1.0: 1.0 to about 2.0: 1.0.
Aspect 11 A method for producing a mixture of terephthalic acid diesters, comprising contacting a first alcohol, a second alcohol and dimethyl terephthalate in the presence of a catalyst, wherein the first alcohol and the second alcohol are different.
Aspect 12 The method of embodiment 11, wherein the first alcohol is n-butanol and the second alcohol is isobutanol.
Aspect 13 The method of embodiment 12, wherein the mixture comprises at least two of n-butyl isobutyl terephthalate, di-n-butyl terephthalate and diisobutyl terephthalate.
Aspect 14. The method according to embodiment 11, wherein the catalyst is a transesterification catalyst.
Aspect 15 The process according to embodiment 14, wherein the catalyst is tetraisopropoxy titanate.
Aspect 16. 12. The method of embodiment 11, wherein the n-butanol and isobutanol are present in an n-butanol / isobutanol molar ratio of about 0.5: 1.0 to about 4.0: 1.0.
Aspect 17 The method of embodiment 16, wherein said n-butanol and isobutanol are present in an amount of n-butanol / isobutanol molar ratio of about 0.75: 1.0 to about 3: 1.0.
Aspect 18. 18. The method of embodiment 17, wherein the n-butanol and isobutanol are present in an amount of n-butanol / isobutanol molar ratio of about 1.0: 1.0 to about 2.0: 1.0.

Claims (4)

n- butyl isobutyl terephthalate, Ri Na comprise terephthalic di -n- butyl and diisobutyl terephthalate, n- butanol, dimethyl isobutanol and terephthalic acid, n- butanol / isobutanol molar ratio of 0.5: 1. A composition prepared by contacting in the presence of a catalyst in an amount of 0 to 4.0: 1.0 . The composition of claim 1 , wherein the catalyst is a transesterification catalyst. The composition of claim 2 wherein the catalyst is tetraisopropoxy titanate. The composition of claim 1 wherein the n-butanol and isobutanol are present in an amount of n-butanol / isobutanol molar ratio of 0.75: 1.0 to 3: 1.0.

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